Detergent compositions containing sulfonio sulfonates



United States Patent 3,390,094 DETERGENT COMPOSITIONS CONTAINING SULFONIO SULFONATES Francis L. Diehl and Howard F. Drew, Wyoming, and Arnon O. Snoddy, Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Mar. 14, 1966, Ser. No. 533,848

Claims. (Cl. 252-138) ABSTRACT OF THE DISCLOSURE Detergent compositions with superior cool Water laundering effectiveness comprising sulfonio sulfonates having a long chain alkyl and an alkaline builder salt.

This invention relates to detergent compositions containing sulfonio sulfonates which are especially effective in cool water. The term cool water as used in describing this invention is intended to mean aqueous washing solutions having a temperature within a range of from about 40 F. to about 95 F. This temperature characterization more generally is intended to mean temperatures substantially below those which are commonly associated with the usual household parlance of hot water.

Some garments or fabrics cannot be washed in hot water, i.e., say in excess of about 110 F., without running the risk. of damaging the material by shrinkage or altering the handle or feel of the fabric or by adversely alfecting dyes or by increasing wrinkling in wash and wear or minimum care garments. For such laundering situations fabric and material manufacturers recommend the use of cool water. Conventional detergents, however, are known to be less effective as cleaning agents, i.e., removing soil, in cool aqueous solutions. There is no question that the presently available detergent compositions can be used under such circumstances but with varying degrees of successful cleaning results. To compensate for the poorer cleaning performance, consumers are generally inclined to use excessive amounts of the detergent compositions. Such economic waste is unfortunate but has been necessary prior to the present invention due to the lack of detergent compositions which are specially formulated to be effective cleaning agents in cool water.

It is an object of this invention to provide a detergent composition which is especially effective in cleaning soiled fabrics in cool aqueous washing solutions and a method for using such a composition in laundering with cool water.

Other objects will be readily apparent to those skilled in the art from a review of the following detailed description of the present invention.

This object of the present invention is achieved with novel built detergent compositions consisting essentially of (1) a sulfonio sulfonate detergent compound having the general formula:

R is an alkyl group containing from 12 to 16 carbon atoms; R is an alkyl or hydroxy alkyl group containing from 1 to 4 carbon atoms; R is C H X wherein n is l, 1 or 2 and X is -H or OH, and (2) a water soluble inorganic alkaline builder salt, an organic alkaline sequestrant builder salt or mixtures thereof, the ratio of weight of the detergent to the builder salt being in the range of from about 4:1 to 1:20.

It has now been surprisingly discovered that certain 3,390,094 Patented June 25, 1968 sulfonio sulfonate compounds having the formula set forth above possess unusually effective cleaning power in aqueous solutions having the cool temperatures defined above. These unexpected cleaning properties of the compounds of this invention are demonstrated by the experimental data presented below. Of the sulfonio sulfonate detergent compounds described herein, best cool Water cleaning results are obtained when R; is dodecyl, R is methyl and R is CH The sulfonio sulfonate compounds to which the present invention pertains can be prepared according to any convenient process. The R alkyl can be derived from synthetic sources such as alkpl bromides, synthetic alcohol, e.g. dodecanol, or from natural sources such as coconut oil or tallow from which fatty alcohols are made. Such processes are noted hereinafter but other methods can be used.

The sulfonio sulfonates can be made by the processes described in US. Patent 2,813,898, issued Nov. 19, 1957, to Van R. Gaertner. An exemplary preparatory equation involving the reaction of propane sultone with methyldodecylsulfide is as follows:

While the class of sulfonate compounds just described can be employed alone as cool water detergent compounds on easily cleanable materials, more outstanding performances are obtained when they are mixed with other ingredients which enhance or build the cleaning power of detergent compounds, i.e., so-called builders or detergency-enhancing compounds. Such built or heavy-duty detergency is essential With hard-to-clean fabrics such as cotton. According to the present invention, therefore, the sulfonate detergent compounds are preferably used in conjunction with such other ingredients which substantially improve cleaning power. While the term builder is used herein in its singular. form, the term is intended to cover mixtures of such compounds also.

The present invention pertains to detergent compositions consisting essentially of a Water soluble inorganic alkaline builder salt or a water soluble organic alkaline sequestrant builder salt, or mixtures thereof, and a member of the class of sulfonate detergent compounds having the general formula described above, which composition consists essentially of the detergent compounds and a builder material in a ratio by weight of detergent to builder of about 4:1 to about 1:20. The preferred ratio of the detergent to builder is 1.1 to about 1:10. The

ratios and percentages referred to herein are all by weight unless otherwise noted.

The built detergent compositions of this invention can be prepared as granular, tablet, or liquid compositions and perform effectively. Within the above detergent to builder ratio range, granular and tablet compositions offering outstanding cool water washing performance can contain from 4% to 50% by weight of the sulfonate detergent compound, the balance comprising essentially a selected builder material or mixtures of builders and any optional ingredients employed. Preferred granular and tablet compositions contain from about 15% to about 35% by weight of the sulfonate detergent with the balance comprising the essential builder materials and other ingredients. On the other hand, built liquid detergents prepared according to the present invention have a slightly modified composition to compensate for the requirement of a liquid vehicle. Such liquid compositions can contain from about 2% to 25% by weight of the sulfonate detergent, preferably from about 8% to about 18%, with the remainder comprised essentially of builder ingredients, and, of course, a liquid vehicle as described below. The ratio set forth above between the detergent and builder applies equally to all physical forms of the composition.

Water soluble inorganic alkaline builder salts which can be used in this invention alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Ammonium or substituted ammonium, e.g., triethanol ammonium, salts of these materials can also be used. Specific examples of suitable salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium and potassium pyrophosphate, sodium and ammonium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium orthophosphate and potassium bicarbonate. The preferred inorganic alkaline builders according to this invention are alkali metal tripolyphosphates for built granular and tablet compositions and alkali metal pyrop'hosphates for built liquid compositions. Potassium is the preferred alkali metal used in liquid compositions and sodium finds best application for granular or tablet compositions.

Examples of suitable organic alkaline sequestrant builder salts used in this invention alone or in admixture are alkali metal, ammonium or substituted ammonium, aminocarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium N-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as organic alkaline sequestrant builder salts (see US. Patent 2,739,942).

Polyphosphonates are also valuable builders in terms of the present invention including specifically sodium and potassium salts of ethane-l-hydroxy-l, l-diphosphonate, sodium and potassium salts of methylene diphosphonate, sodium and potassium salts of ethylene diphosphonate, and sodium and potassium salts of ethane- 1,l,2-triphosphonate. Other examples include the alkali metal salts of ethane-Z-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-1,1,2-triphosphonic acid, ethane- Z-hydroxy- 1, 1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-l,2,2,3-tetraphosphonic acid.

Besides the builders being used in the form of mixtures it is also possible according to the present invention to use the sul'fonio sulfonate compounds of this invention in combination with other cleaning agents such as anionic, nonionic, ampholytic and zwitterionic organic detergent surfactant compounds. When it is desired to use such sulfonate compounds in combination with other detergent compounds, they are preferably utilized with anionic detergents because of the sudsing characteristics of the latter. The ratio of the sulfonate to such other detergent compound is about :1 to 1:5. If it is desired to use such a sulfonio sulfonate in admixture with another detergent compound as the active portion of a cleaning composition, the ratio of such a mixture to the builder salt should be Within the previously prescribed range of 4:1 to 1:20. A composition prepared along these lines can contain from 4% to 50% of such mixture and 5% to 85% of a builder salt selected from water soluble inorganic alkaline builder salts, water soluble organic sequestrant builder salts, and mixtures thereof, within the prescribed ratio range.

Examples of anionic soap detergents which can be used in admixture with the sulfonate detergent, if desired, are the sodium, potassium, ammonium and alkylolammonium salts of higher detergent range fatty acids (C -C Prati-cularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of suitable anionic organic non-soap detergents in the form of their water soluble salts are: alkylglycerylether sulfonates; alkyl sulfates; alkylmonoglyceride sulfates or sulfonates; alkylpolyethenoxyether sulfates; acylsarcosinates; acyl esters of isothionates; N-acyl-N-methyl taurides, alkylbenzenes sulfonates wherein the alkyl substituent is straight chain or branched chain; sulfonated a-OlGfiIlS; alkylphenol polyethe-noxy sulfonates. In these compounds the alkyl and acyl groups, respectively, contain 10 to 20 carbon atoms. They are used in the form of water soluble salts, the sodium, potassium, ammonium, and alkylolammonium salts, for example. Specific examples are: sodium lauryl sulfate, sodium tallow alkyl sulfate; sodium salt of sulfonated on tridecene; potassium N-methyl-N-lauroyl tauride; triethanolammonium tetrapropylbenzene sulfonate; sodium (linear) dodecyl benzene sulfonate.

Examples of nonionic organic detergents which can be used in the compositions of this invention, if desired, are: polyethylene oxide condensates of alkylphenols wherein the alkyl group contains from 8 to 15 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkylphenol in the range of 8:1 to 20:1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products ranges from 5000 to 11,000; the condensation products of from about 5 to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms, e.g., condensation product of 6 moles of ethylene oxide with one mole of lauryl alcohol; higher alkyl di-lower alkyl amine or phosphine oxides, e.g., dodecyldimethylamine oxide or dodecyldimethyl phosphine oxide; alkyl methyl sul-foxides such as dodecyl methyl sulfoxide.

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are sodium 3- dodecylaminopropionate, 3-(N methyl N hexadecylamine)-2-hydroxypropane-l-sulfonate and its dodecylhomology, sodium 3-dodecylamino-propane sulfonate, dodecyl-beta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of United States Patent No. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of United States Patent Number 2,43 8,091, and the products sold under the trade name Miranol and described in United States Patent No. 2,528,378.

Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 18 carbon atoms and one contains an anionic water solubilization group, e.g., carboxy, sulfo, or sulfato. Examples of compounds falling within this definition are: 3- (N,N-dimethyl-N-hexadecylammonio) 2 hydroxypropane-l-sulfonate and the corresponding dodecyl and tetradecyl homologs and 3-(N,N dimethyl N dodecylammonio)-propane-1-sulfonate and the corresponding hexadecyl and tetradecyl homologs.

The discovery that the compositions containing members of the class of compounds described in this invention show exceptional cool Water detergency was unpredictable in view of the fact that there is, as yet, virtually no generally accepted theory or background information on the mechanics of cool water detergency. Moreover, cleaning agents such as sodium tallow alcohol sulfate or sodium dodecylbenzenesulfonate, for example, which are good hot water (130-140 F.) detergent compounds exhibit a minimum of cleaning activity in cool water. One would be led to assume that the sulfonate compounds of the present invention should be, comparatively speaking, as poor as any other conventional detergent compounds when used in cool water; certainly there is no reason to except that they would behave otherwise. As has been discovered, however, the compositions containing the sulfonate compounds of this invention are substantially more effective in cool water than some of the commonly used commercially available detergent compositions are in hot water. It can, therefore, be seen that the structure of a given detergent compound which is effective in hot water has little or no discernible relation to the effectiveness of such compounds in cool water.

It has also been found that maximum cleaning occurs with the compositions of this invention when the pH of the washing solution, at cool water temperatures as here: in defined is within the range of from about 8 to about 12 with the preferred pH range being 9.5 to 11.5. Using normal amounts of water for washing, the desired pH of the solution can be obtained by incorporating into the compositions of this invention a normal amount of a strongly alkaline material such as sodium silicate, i.e., up to about by weight. The silicate acts as a buffer and also as a corrosion inhibitor.

A laundering method incorporating the discovery of the present invention can be practiced in a number of different ways. Preferably the Washing step is followed by rinsing and drying the fabrics. The washing solution can be prepared by adding the granular, tablet or liquid detergent composition prepared according to this invention to any container which contains cool water at a temperature ranging from about 40 F. to about 95 F., usually about 80 F. The detergent composition concentration in solution can range from about 05% to .50% by total weight in the usual washing operation, and should be added in sufiicient amount to provide a concentration of at least 0.005% of the sulfonio sulfonate detergent compound. The fabrics can be added to the container or washer before or after the washing solution is added. As is usual in a washing step, the fabrics are then agitated in the detergent solution. While the period of time may vary, an automatic agitator type washer, generally employs a washing cycle which ranges from 8 to 15 minutes. In special situations, such as hand washing in basins, pools or streams, higher composition concentrations can be employed, including solutions or pastes of up to 5%, or even 50% and higher.

After the washing step, the washing liquor is drained off or the fabrics are separated from the liquor and thereafter the fabrics are rinsed in clean water. The fabrics can be rinsed as many times as desired in order to insure that washing liquor is removed. Using an automatic washer, it has been found that about four spray rinses and one deep rinse are usually sufiicient for this purpose. Between and after rinsing steps, the bulk of the rinse water is usually drawn from or spun out of the fabrics. After rinsing, the fabrics are dried. Although rinsing and drying are usual and desirable steps, the important advantage of the invention is achieved in the washing step.

The surprisingly effective cool water performance characteristics of the sulfonio sulfonate compounds described herein are demonstrated by conducting the following tests.

Naturally soiled fabric swatches (desized cotton print cloth) were washed for ten minutes in an aqueous solution of a detergent composition having a pH of 10 and containing 7 grains equivalent CaCO hardness per gallon. Detergent compositions were prepared containing only basic essentials, i.e., a detergent compound and a builder compound. The detergent compounds were respectively (1) a representative sulfonio sulfonate and (2) sodium tetrapropylenebenzene sulfonate (ABS); the builder compound in each composition was sodium tripolyphosphate.

The sulfonate compound was 3-(S-dodecyl, S-methyl sulfonio)propane-l-sulfonate (DMSPS). By using the same builder compound in each composition, any variations in cleaning performance could be directly attributed to the specific detergent being evaluated. The concentration by weight in the washing solution of the detergent compound was 03%; the concentration of the builder was .06%.

These two compositions were compared for their soil removal properties, the sulfonio sulfonate in a washing solution at F. and the ABS in a washing solution at 140 F. and 80 F. Soil removal, expressed as a percentage of the soil originally present on the soiled swatches, was determined. The amounts of soil present (a) on the cloth swatches after washing and drying and (b) on similar unwashed swatches were determined by solvent extraction.

Compound Temperature, F. Soil Removal, percent Test 1 A 140 65 63 S 80 42 fir ts-s i" l 0 Test 3: 67 ABS 140 64 DMSPS 140 75 The sulfonio sulfonate detergent compounds gave results, in this test, in water at 80 F. which were as good as or superior to the results obtained with a formula wherein sodium tetrapropylenebenzene sulfonate (ABS) was used as a cleaning agent in a washing solution having a temperature of 140 F. Sodium tetrapropylenebenzene sulfonate is widely regarded as a standard for comparison. Compositions which perform better than ABS at 140 F. generally can find application and commercial acceptance as detergent formulations. In situations such as the present invention where superior cleaning is obtained with different compounds at low temperatures, i.e., 80 F. the results are even more remarkable.

The same superiority of the sulfonio sulfonate compounds at 80 F. over ABS at 140 F. was demonstrated in a similar washing test employing soiled mens white dress shirts where the collars and cuffs were used as the basis for comparing cleaning ability of compositions employing these two detergent compounds. The superior cleaning ability of the sulfonio sulfonate compounds was pagicularly manifested in the whiteness of the collars and cu s.

Substantially the same performance advantages are observed by the housewife when doing the home laundry in water ranging from 40 to 95 F. Woolens and synthetic fibers washed in the same manner are cleaned as etficiently when washed according to .the process of this invention and using the compositions of this invention as they would be if they were washed in conventional detergent compositions at hot water temperatures, yet a minimum of shrinkage and wrinkling takes place and the feel of the wool is preserved to a greater extent.

While the compositions of this invention are outstandingly effective in water at a temperature ranging from 40 F. to F. Below about 60 F. it has been found that the granular detergent compositions of this invention are somewhat slower to dissolve, consequently it is preferred to use liquid compositions at such lower temperatures.

The following compositions further illustrate the manner in which the invention can be practiced; they provide improved cool water detergency characteristics similar to that demonstrated in the soil removal comparison set forth above. The pI-Is of each of the compositions in aqueous solution ranged from 9.5 to 1.1.5 at concentrations of about 0.25%. Included are both liquid and granular formulations. Mixtures of the sulfonio sulfonates and other detergents can be used. The examples are not to be construed as limiting the scope of the invention claimed hereinafter. These compositions are useful in automatic washers and conventional type washers employing cool water, 40 F. to 95 F., as well as hand washing operations.

EXAMPLE I Solid-Granules Percent 3 (S-dodecyl, S-butyl sulfonio) propane 1 sulfonate 17.5 Sodium tripolyphosphate 50 Sodium silicate (N21 O:SiO =l:2.5) 10.0 Sodium sulfate 17.5 Moisture 5.0

EXAMPLE II Compressed granules-Tablet Percent 3-(S-tetradecyl, S-ethyl sulfonio) propane 1 sulfonate 31 Tetrasodium pyrophosphate 52 Trisodium phosphate Moisture 7 EXAMPLE III Solid-Granules Percent 2-(S-hexadecyl, S-2-hydroxyethyl sulfonio) ethane-1- sulfonate 32 Trisodium ethane-l-hydroxy-I,1,2-triphosphonate 64 Moisture 4 EXAMPLE IV Solid-Granules Percent 3-(N,N dimethyl-N-hexadecylammonia)-propane-lsulfonate 3-(S-dodecyl, S-propyl sulfonio)-2-hydroxypropanel-sulfonate Sodium tripolyphosphate Sodium carbonate 10 Sodium silicate (Na O:SiO =1:2.5) 5 Moisture 5 EXAMPLE V Solid-Granules Percent 3-(S-dodecyl, S-methyl sulfonio) propane 1 sulfonate 20 Sodium tallow alcohol sulfate 10 Trisodium ethane-l-hydroxy-1,1-diphosphonate 20 Sodium tripolyphosphate 10 Sodium nitrilotriacetate 10 Sodium sulfate 8 Sodium silicate (N21 O:SiO =1:2.5) 11 Moisture 11 EXAMPLE VI Liquid Percent 4-(S-dodecyl, S-methyl) 2 hydroxybutane-l-sulfonate 5.0 Sodium salt of S0 sulfonated 1:1 weight mixture of dodecene and a-tetradecene 10.0 Tetrapotassium pyrophosphate 19.0 Sodium silicate (Na O:SiO =1:l.6) 3.8 Potassium toluene sulfonate 8.5 Carboxymethyl hydroxyethyl cellulose .3 Water Bal.

Water Bal.

EXAMPLE VIII Solid-Granu1es Percent 4-(S-dodecyl, S-propyl sulfonio)butane-1-sulfonate 5 Condensation product of 10 moles of ethylene oxide and one mole of tallow fatty alcohol 5 Sodium (linear) tridecyl benzene sulfonate 10 Dodecyldimethyl phosphine oxide 5 Coconut oil soap 5 Sodium tripolyphosphate 50 Tetrasodium ethylenediamine tetraacetate 20 It will be appreciated that the sulfonio sulfonate compounds used in the present invention can be incorporated into many other liquid or granular detergent composi tions with suitable adjustments being made in the other components.

Materials which are considered normal and desirable additives in liquid or granule detergent compositions can be added to the compositions of this invention without adversely affecting or modifying basic cleaning characteristics. For example, a tarnish inhibitor such as benzotriazole or ethylene thiourea may be added in amounts up to about 1%. Fluorescers, perfume, bleaching agents, color, antiredeposition agents, antibacterial agents, thickening agents, opacifiers, and blending or viscosity control agents, while not essential in the compositions of this invention, may also be added.

While the present invention finds exceptional application in cool water washing situations, the compositions described herein can also be used in conjunction with warm and hot water.

What is claimed herein is:

1. A detergent composition having superior cleaning ability in aqueous solutions having a temperature within a range of from about 40 F. to about F. consisting essentially of (1) a sulfonate detergent compound of the following general formula:

R is an alkyl group containing from 12 to 16 carbon atoms; R is an alkyl or hydroxy alkyl group containing from 1 to 4 carbon atoms; R is C H X wherein n is 0, 1 or 2 and X is H or --OH and (2) a builder material selected from the group consisting of water soluble inorganic alkaline builder salts, organic alkaline sequestr-ant builder salts, and mixtures thereof, the ratio by weight of said detergent compound to said builder material being in the range of about 4:1 to about 1:20.

2. The detergent composition of claim 1 wherein the ratio of said detergent compound to said builder is from 1:1 to about 1:10, by weight.

3. The detergent composition of claim 2 in which the aqueous solution has a pH of from about 8 to about 12.

4. The detergent composition of claim 3- wherein the preferred pH range is between about 9.5 and 11.5.

5. The detergent composition of claim 3, wherein, said builder material is sodium tripolyphosphate.

6. The detergent composition of claim 3 wherein the detergent compound is (S-dodecyl, S-methyl sulfonio)- propane-l-sulfonate.

7. The detergent composition of claim 5 wherein the detergent compound is (S-dodecyl, S-methyl su1fonio)- propane-l-sulfonate.

8. A laundering process comprising the steps of immersing soiled fabrics and garments into an aqueous solution having a temperature within the range of from about 40 F. to about 95 F., and a pH of from about 8 to about 12, said aqueous solution containing at least about .05% by weight of the detergent composition of claim 1 9. The process of claim 8 wherein the detergent composition is that of claim 5.

10. A built detergent composition consisting essentially of 4 to 50% of a mixture of the sulfonate detergent compound of claim 1 and an organic anionic detergent, the ratio of the compound to said organic detergent being 10 in the range of 10:1 to 1:5 and from 5 to 85% of a builder material selected from the group consisting of Water soluble inorganic alkaline builder salts, water soluble organic alkaline sequestrant builder salts, and mixtures thereof.

References Cited UNITED STATES PATENTS 2,799,702 7/1957 Gaertner 260-513 2,813,898 11/1957 Gaertner 26050-5 3,190,891 6/1965 Baird et al. 260327 LEON D. ROSDOL, Primary Examiner.

P. E. WILLIS, Assistant Examiner. 

